Novel (UV absorbing compounds and) photographic elements containing UV absorbing compounds

ABSTRACT

1-Amino-4-cyano-1,3-butadiene compounds of the formula ##STR1## wherein n is 1 or 2, when n is 1 R 1  and R 2  can be the same or different and represent hydrogen, alkyl including substituted alkyl, aryl including substituted aryl or cyclic alkyl groups, except that both R 1  and R 2  cannot be hydrogen, or taken together R 1  and R 2  represent the elements necessary to complete a cyclic amino group and when n is 2 at least one of R 1  and R 2  is alkylene or arylene; G represents an electron withdrawing group. The compounds are especially useful in photographic elements as UV absorbers.

This .Iadd.is an application for reissue of U.S. Pat. No. 4,045,229,based on U.S. Ser. No. 641,788, filed Dec. 18, 1975, which .Iaddend.is acontinuation-in-part of our .[.co-pending.]. application Ser. No.506,913, filed Sept. 17, 1974, now abandoned.

This invention relates to 1-amino-4-cyano-1,3-butadiene compounds usefulas filter compounds and to photographic elements containing saidcompounds.

The compounds of the invention absorb ultraviolet (UV) light and haveproperties which make them useful filter dyes. Although the UV absorbingcompounds of the invention appear to be primarily useful with respect tocolor films and papers containing photoreducible silver halide; ifdesired, they can be incorporated in black-and-white films which containphoto-reducible silver halide. They may also be used in other areaswhere protection from UV light is needed, such as in the plasticsindustry. Protection from UV light can be obtained by incorporating theUV absorbing compounds of this invention into the body of or the surfaceof the plastic item being protected.

As is known to those skilled in the photographic art silver halideemulsions are sensitive to ultraviolet light. Color films such asKodachrome and Ektachrome Films, for example, would be adverselyaffected by ultraviolet light unless protected therefrom. To illustrate,if ultraviolet light is not substantially prevented from reaching thesilver halide-containing layers of a color film, such as those justmentioned, the film will be more bluish than it should be. Snow andblacktop driveways, for example, would have an unnatural bluish cast orappearance in photographs made using film that has no UV absorbingfilter layer.

From the foregoing brief discussion it will be apparent that to obtaincolor pictures of true color rendition, ultraviolet light should beprevented from reaching the silver halide-containing layers of the colorfilm.

Various materials have been examined for use as UV absorbers inphotographic elements, particularly in the overcoats of such elements.UV absorbers which are water-soluble may diffuse during coating andprocessing to other layers of the photographic element and thus cansometimes interfere with various photographic functions. On the otherhand, when water-insoluble UV absorbers are evaluated, a cosolvent isusually required for dispersion into a photographic emulsion and theresulting system is not always stable, i.e., an oil-phase oftenseparates on standing. Upon coating, the dye aggregates, and the coatedlayer shows a new, unwanted absorption shoulder.

The prior art method of dispersing water-insoluble substances into anaqueous gelatin coating composition which was preferred heretoforeinvolved dissolving the substance in (i) a high boiling organic solvent(which will not evaporate from the coated layer), and (ii) optionallywith an auxiliary solvent, and then milling the solution with an aqueousgelatin solution in a colloid mill for a considerable time to produce asatisfactory coating composition. The dispersion then had to be noodledand washed to remove the auxiliary solvent. This was a complicated,time-consuming, inefficient, heat-generating process. Further, theresulting dispersions tended to coagulate, aggregate, or crystallize,and the oil in the coated layers derived therefrom tended to migrate ordiffuse to other layers.

In one aspect this invention relates to a photographic elementcomprising a support having thereon at least one radiation sensitivesilver halide emulsion layer and a 1-amino-4-cyano-1,3-butadieneultraviolet absorbing compound.

In another aspect this invention relates to a photographic elementcomprising a support having thereon at least one radiation sensitivesilver halide emulsion layer and an ultraviolet filter layer comprisinga binder and at least one compound having the formula: ##STR2## whereinn is 1 or 2, when n is 1, R₁ and R₂ can be the same or different andrepresent hydrogen, cyano, alkyl of 1 to 10 carbon atoms includingsubstituted alkyl such as cyanoalkyl, alkoxyalkyl, aryl of 6 to 20,preferably of 6 to 10 carbon atoms including substituted aryl or cyclicalkyl groups of 5 to 6 carbon atoms, except that both R₁ and R₂ cannotbe hydrogen, or taken together R₁ and R₂ represent the elementsnecessary to complete a cyclic amino group such as, for example,piperidino, morpholino, pyrrolidino, hexahydroazepino and piperazinogroups, and when n is 2 at least one of R₁ and R₂ can be alkylene orarylene; G represents an electron withdrawing group. Any of the electronwithdrawing groups known in the art can be used according to thisinvention. Preferred electron withdrawing groups include ##STR3## whereR represents an alkyl group of 1 to 10 carbon atoms or an aryl group of6 to 20, preferably 6 to 10 carbon atoms.

In yet another aspect, this invention relates to a photographic elementcomprising at least one silver halide emulsion layer coated on a filmsupport, said film support having incorporated therein at least oneultraviolet filter compound of the formula: ##STR4## wherein n is 1 or2, when n is 1, R₁ and R₂ can be the same or different and representhydrogen, cyano, alkyl of 1 to 10 carbon atoms including substitutedalkyl such as cyanoalkyl, alkoxyalkyl, aryl of 6 to 20, preferably of 6to 10 carbon atoms including substituted aryl or cylic alkyl groups of 5or 6 carbon atoms, except that both R₁ and R₂ cannot be hydrogen, ortaken together R₁ and R₂ represent the elements necessary to complete acyclic amino group such as, for example, piperidino, morpholino,pyrrolidino, hexahydroazepino and piperazino groups, and when n is 2 atleast one of R₁ and R₂ can be alkylene or arylene; G represents anelectron withdrawing group such as ##STR5## where R represents an alkylgroup of 1 to 10 carbon atoms or an aryl group of 6 to 20, preferably 6to 10 carbon atoms.

In still yet another aspect, this invention relates to novel ultravioletabsorbing compounds having the general formula: ##STR6## wherein n is 1or 2, when n is 1, R₁ and R₂ can be the same or different and representhydrogen, cyano, alkyl of 1 to 10 carbon atoms including substitutedalkyl such as cyanoalkyl, alkoxyalkyl, aryl of 6 to 20, preferably of 6to 10 carbon atoms including substituted aryl or cyclic alkyl groups of5 or 6 carbon atoms, except that both R₁ and R₂ cannot be hydrogen, ortaken together R₁ and R₂ represent the elements necessary to complete acyclic amino group such as, for example, piperidino, morpholino,pyrrolidino, hexahydroazepino and piperazino groups, and when n is 2 atleast one of R₁ and R₂ can be alkylene or arylene; G represents anelectron withdrawing group such as ##STR7## where R represents an alkylgroup of 1 to 10 carbon atoms or an aryl group of 6 to 20, preferably 6to 10 carbon atoms.

The new compounds of this invention are useful as ultraviolet filterabsorbers which have high absorptive capability. Our UV absorbingcompounds are generally low melting solids and are pure in the liquidstate. The compounds of the present invention absorb strongly up to 400nm. and have little absorption beyond 400 nm. They are unexpectedlystable when exposed to heat. In the liquid state they are hydrophobic,but may be incorporated directly into an otherwise conventionalpolymeric photographic support. Our compounds can also be used with abinder as a coating composition which can be coated onto a photographicsupport as a separate layer, without the use of special or auxiliarysolvents if desired.

The reaction used in preparing the compounds of our invention isconventionally carried out by treating an appropriate primary orsecondary amine with an appropriate intermediate in absolute alcohol atrefluxing temperature of the resulting solution followed usually bydistillation of the product under reduced pressure. The compounds areobtained in good yield and high purity.

In one form, the present invention is directed to a photographic supporthaving incorporated therein at least one UV absorbing compound havingthe structure of formula 1. In order to use materials for UV protectionof a photographic element when the materials are incorporated within thesupport, it is generally desirable that the support be transparent, andit is usually preferred that the support be substantially colorless. Avariety of conventional transparent photographic film supports are knownto the art into which the UV absorbing compounds of this invention canbe incorporated. Photographic supports can be broadly categorized forpurposes of this discussion into those that can be solvent cast andthose that are formed from a melt. The UV absorbing compounds of thisinvention are stable and can be incorporated into the photographicelement without use of a special or auxiliary solvent. To incorporateour UV absorbing compounds into a solvent-cast film support, such as acellulosic support--e.g., one composed of cellulose nitrate, cellulosediacetate, cellulose triacetate, etc.--it is merely necessary todissolve the compound in the casting solution employed in themanufacture of the support. Our UV absorbing compounds can beincorporated into melt-formed polymeric film supports merely bydispersing the dye within the molten polymer. Since our UV absorbingcompounds possess a surprising degree of thermal stability they can beincorporated into melt-formed film support materials such aspolyalkylene (e.g. polyethylene), polystryene, phthalic acid polyesterssuch as poly(ethylene terephthalate), polycarbonates as well as other,lower melting, resinous polymers useful in forming film supports. It isgenerally preferred that our UV absorbing compounds be substantiallyhomogeneously dispersed within the film support so as to exhibit uniformoptical density upon viewing the support. This can be readily achievedby thoroughly mixing the UV absorbing material with the support material(prior to its being formed into a support) using procedures well knownin the art.

When the UV absorbing compound is coated onto a support rather thanbeing incorporated therein, it is, of course, possible to employ anyconventional photographic support. The support can be opaque totransparent. The support can have any one of a variety of diverse forms,such as a glass, metal, film, wood, paper or composite (e.g. resincoated paper) support. To immobilize spatially the UV absorbing materialon the support it is generally preferred that the UV absorber beincorporated within a transparent layer containing a binder, which layeris directly associated with the support. Sometimes the binder can be thesame type of polymer as that which comprises the support. The compoundcan also be incorporated into any photographic binder layer as desired.Generally, any conventional transparent binder can be used. Anespecially useful class of binders are the latexes disclosed in ChenU.S. application Ser. No. 506,919 filed Sept. 17, 1974. In this ChenU.S. application is also disclosed a valuable method for incorporatingthe UV absorbing compounds of this invention into a photographic elementor emulsion. Hydrophilic colloids such as gelatin can also be used as abinder material if desired. The binder layer(s) containing one or moreof the UV absorbing compounds of this invention can be located directlyon the support or can be separated by one or more undercoats providedfor the purpose of improving adhesion to the support. Such binderlayer(s) can also be present as overcoats or protective layer(s)overlying or between the light-sensitive emulsion layer(s) if desired.Binder layers containing one or more UV absorbing compound can be coatedboth as an underlayer as well as an overcoat layer on a single supportif desired. Other suitable photographic vehicles useful as binders andlayer arrangements are described in Product Licensing Index, Vol. 92,December 1971, publication 9232, page 108, paragraph VIII, hereincorporated by reference. Generally, the UV absorbing compounds in thebinder layer as contemplated herein are chosen to provide opticaldensities similar to those set forth above for UV absorbing compoundsincorporated into the support. Optically homogeneous dispersion of thedye in the binder is preferred and can be obtained without the use ofauxiliary solvents. This can be achieved by the techniques disclosed inthe aforementioned Chen application as well as techniques which are wellknown to those skilled in the art.

This invention may be used with photographic elements which containsilver halide emulsions. The 1-amino-4-cyano-1,3-butadiene compounds mayalso be incorporated in the silver halide emulsion layer. The silverhalide emulsions can comprise, for example, silver choride, silverbromide, silver bromoiodide, silver chlorobromide, silver chloroiodide,silver chlorobromiodide, crystals or mixtures thereof. The emulsions canbe coarse or fine grain emulsions and can be prepared by a variety oftechniques, e.g., single jet emulsions such as those described inTrivelli and Smith The photographic Journal, Vol. LXXIX, May, 1939 (pp.330-338), double jet emulsions such as Lippmann emulsions, ammoniacalemulsions, thiocyanate or thioether ripened emulsions such as thosedescribed in Nietz et al U.S. Pat. No. 2,222,264 issued Nov. 91, 1940;Illingsworth U.S. Pat. No. 3,320,069 issued May 16, 1967 and McBrideU.S. Pat. No. 3,271,157 issued Sept. 6, 1966. Silver halide emulsionscan form latent images predominantly on the surface of the silver halidegrains, or predominantly on the interior of the silver halide grainssuch as those described in Davey et al U.S. Pat. No. 2,592,250 issuedMay 8, 1952; Porter et al U.S. Pat. No. 3,206,313 issued Sept. 14, 1965;Berriman U.S. Pat. No. 3,367,778 issued Feb. 6, 1968 and Bacon et alU.S. Pat. No. 3,447,927 issued June 3, 1979. If desired, mixture of suchsurface and internal image-forming emulsions can be made, such as beingdescribed in Luckey et al. U.S. Pat. No. 2,996,382 issued Aug. 15, 1961.Silver halide emulsions can be regular grain emulsions such as the typedescribed in Klein and Moisar, J. Phot. Sci., Vol. 12, No. 5,September/October, 1964, pp. 242-251 and German Pat. No. 1,207,118.Negative type emulsions can be made, as well as direct positiveemulsions as described in Leermakers U.S. Pat. No. 2,184,013 issued Dec.19, 1939; Kendall et al U.S. Pat. No. 2,541,472 issued Feb. 13, 1951;Schouwenaars British Pat. No. 723,019 issued Feb. 2, 1955; Illingsworthet al French Pat. No. 1,520,821 issued Mar. 4, 1968; Illingsworth U.S.Pat. No. 3,501,307 issued Mar. 17, 1970; Ives U.S. Pat. No. 2,563,785issued Aug. 7, 1951; Knott et al U.S. Pat. No. 2,456,953 issued Dec. 21,1948 and Land U.S. Pat. No. 2,861,885 issued Nov. 25, 1958.

In one preferred form, the 1-amino-4-cyano-1,3-butadiene compounds maybe used with elements designed for color photography, for example,elements containing silver halide emulsion and color-forming couplerssuch as those described in U.S. Pat. Nos. 2,376,679 by Frohlich et al.,2,322,027 by Jelley et al, 2,801,171 by Fierke et al., 2,698,794 byGodowsky, 3,227,554 by Barr et al, and 3,046,129 by Graham et al.; orelements to be developed in solutions containing color-forming couplerssuch as those described in U.S. Pat. Nos. 2,525,718 by Mannes et al.,2,592,243 by Carroll et al and 2,950,970 by Schwan et al.; and infalse-sensitized color materials such as those described in U.S. Pat.No. 2,763,549 by Hanson.

In another form this invention may be used with elements such asdescribed in U.S. Pat. No. 3,761,276 by Evans and in U.S. Pat. No.2,716,059 by Yutzy et al; silver salt diffusion transfer systems whereindevelopment of silver halide precedes solution of the silver halide withprocesses as described in U.S. Pat. Nos. 2,352,014 by Rott, 2,543,181 byLand, 3,020,155 by Yackel et al and 2,861,885 by Land; colorimage-transfer processes such as described in U.S. Pat. Nos. 3,087,817,3,185,567 and 2,983,606 by Rogers, 3,253,915 by Weyerts et al.,3,227,550 by Whitmore et al., 3,227,551 by Barr et al., 3,227,552 byWhitmore, 3,415,644, 3,415,645 and 3,415,646, all by Land, 2,543,181 and3,635,707, Canadian Pat. No. 674,082 and Belgian Pat. Nos. 757,959 and757,960, both issued Apr. 23, 1971; and imbibition transfer processes asdescribed in U.S. Pat. No. 2,882,156 by Minsk; all of which areincorporated herein by reference.

In photographic elements intended for use in color photography, the UVabsorbing compounds of this invention are preferably used in a binderlayer as an overcoat over the light-sensitive layer(s) to be protected.The UV absorbing compounds may also be used as an interlayer i.e. alayer provided under the layer(s) that do not require protection. The UVcompounds may also be incorporated into the support or the support maybe provided with a UV absorbing filter layer before the light-sensitiveemulsion layer(s) are applied thereto in order to minimize thereflectance of light from the surface of the support or to protect theemulsion layer if the element is exposed through a transparent support.

The following examples further illustrate the invention.

PREPARATION OF INTERMEDIATES

A. The intermediate 3-acetanilidoallylidenemalononitrile ##STR8## wasprepared by heating at reflux for 10 minutes, malononitrile (50 g.) with3-anilinoacroleinanil hydrochloride (186 g.) in acetic anhydride (600ml.). The solution was then cooled and filtered and the solid washed inmethanol. The product was recrystallized from acetic anhydride, filteredand the solid washed with methanol and dried. Yield 110 g.

B. The intermediate 3-methoxyallylidenemalononitrile ##STR9## wasprepared by heating at reflux of 1 hour malononitrile (132 g., 2.0 mole)and trimethoxypropene (270 g. 2.0 mole) in 250 ml. of butyronitrile. Thesolution was then cooled in dry ice and the product was obtained. Yield65 g. 25%.

PREPARATION OF UV ABSORBING COMPOUNDS

A. 3-Dibutylaminoallylidenemalononitrile ##STR10##

Dibutylamine (15.0 g. 0.116 mole) was refluxed for 20 minutes with theintermediate of Example A 3-acetanilidoallylidenemalononitrile (11.9 g.,0.05 mole) in ethanol (50 ml.). The ethanol was then distilled off andthe product obtained by distillation at 157° C. and 3μ. M.W. 231.33 C₁₄H₂₁ N₃, Yield 5.0 g. (45%).

B. 3-Dihexylaminoallylidenemalononitrile ##STR11##

Dihexylamine (20.0 g, 0.108 mole) was refluxed for 20 minutes with3-acetanilidoallylidenemalononitrile (11.9 g, 0.05 mole) in ethanol (50ml). The ethanol was then distilled off and the product obtained bydistillation at 170° C. at 5μ. M.W. 287.43, C₁₈ H₂₉ N₃, Yield 4.8 g(33%).

C. 3-Tert-butylaminoallylidenemalononitrile ##STR12##

Tert-butylamine (50 g, 0.68 mole) was refluxed for 15 minutes with3-acetanilidoallylidenemalononitrile (6.0 g, 0.29 mole) in ethanol (300ml). The compound precipitated from the reaction mixture after chillingand was purified by recrystallization from ethanol. M.W. 175.24, Yield15.0 g. (30%).

D. 3-Diisobutylaminoallylidenemalononitrile ##STR13##

Diisobutylamine (25 g, 0.20 mole) was refluxed for 15 minutes with3-acetanilidoallylidenemalononitrile (23.0 g, 0.10 mole) in ethanol (50ml). The ethanol was then distilled off and the product obtained bydistillation at 124°-160° and 4μ. M.W. 231.33, C₁₄ H₂₁ N₃, Yield 9.5 g(41%).

E. 3-Di-sec-butylaminoallylidenemalononitrile ##STR14##

Di-sec-butylamine (25 g, 0.20 mole) was refluxed for 20 minutes with3-acetanilidoallylidenemalononitrile (23.0 g., 0.10 mole) in ethanol(100 ml). The ethanol was then distilled off and the product obtained bydistillation at 150° C. and 6μ. M.W. 231.33, C₁₄ H₂₁ N₃, Yield 4.9 g(20%).

F. 3-Hexahydroazepinoallylidenemalononitrile ##STR15##

Hexahydroazepine (20.0 g, 0.2 mole) was refluxed for 15 minutes with3-acetanilidoallylidenemalononitrile (11.9 g, 0.05 mole) in ethanol (50ml). The ethanol was then distilled off and the product obtained bydistillation at 150°-180° at 3μ. M.W. 201.24, C₁₂ H₁₅ N₃, Yield 2.5 g(25%).

G. 3-N(n-butyl)-N-cyanomethyl aminoallylidenemalononitrile ##STR16##N-butyl-N-cyanomethylamine (13 g.) was heated with the intermediate ofExample B, 3-methoxyallylidenemalononitrile (13.4 g.). The solution wasthen distilled with the fraction boiling at 140°-172° at 8μ collected.Yield 11.5 g.

The following compounds (H-L) were prepared using the intermediate ofExample A with the following amines:

(a) Bis(2,2-diethoxyethyl)amine

(b) N-cyanomethyl-N-methylamine hydrochloride

(c) Piperazine

(d) N,N'-Diethyl-1,6-hexanediamine

(e) Bis(2-cyanoethyl)amine

H. 3[N,N-Bis-(2,2-diethoxyethyl)amino]allylidenemalononitrile ##STR17##

I. 3(n-methyl-N-cyanomethyl)aminoallylidenemalononitrile ##STR18##

J. 1,4-Piperazino bis(allylidenemalononitrile) ##STR19##

K. N,N'-diethyl-N,N-di-(4,4-dicyanobutadienyl)-1,6-diaminohexane##STR20##

L. 3-[N,N-bis(2-cyanoethyl)amino]allylidenemalononitrile ##STR21##

Compounds M-P were prepared by refluxing together three reactants, theappropriate amine, the appropriate sulfonylacetonitrile and1,1,3-trimethoxypropene. The particular reactants used are in Table Ibelow. Compounds N, O and P precipitated during refluxing or onsubsequent cooling. Compounds N and O were treated with additionalalcohol, ethanol or isopropanol, so that the precipitate could befiltered easily. Compound N was purified by dissolving the compound incresol and reprecipitating it by addition of methanol. Compound O waspurified by passing a methanol/acetonitrile solution of the compoundthrough a column containing Amberlyst® ion exchange resin. Compound Pwas washed with ether and purified by redissolving the compound inacetone, adding ether until the solution turned cloudy, and thenchilling the suspension for 72 hours before filtering off the purifiedcompound. Compound M was more difficult to isolate. It did notprecipitate directly from the reaction mixture. A portion of thereaction mixture was removed, stirred with ether until crystals formedand these were then used as seed crystals for the reaction mixture.Ethanol was added, the product was filtered off and recrystallized frommethanol.

M. 3-Morpholinoallyidene methylsulfonylacetonitrile ##STR22##

N. 3-Morpholinoallylidene 4-tert-butylphenylsulfonylacetonitrile##STR23##

O. 3-Piperazinoallylidene 4-tert-butylphenylsulfonylacetonitrile##STR24##

P. 3-N-methylpiperazinoallylidene 4-tert-butylphenylsulfonylacetonitrile##STR25##

                  Table 1                                                         ______________________________________                                        Compound Amine         Sulfonylacetonitrile                                   ______________________________________                                        M        Morpholine    Methylsulfonylacetonitrile                             N        Morpholine    4-t-butylphenylsulfonyl-                                                      acetonitrile                                           O        Piperazine    4-t-butylphenylsulfonyl-                                                      acetonitrile                                           P        N-Methyl-     4-t-butylphenylsulfonyl-                                        piperazine    acetonitrile                                           ______________________________________                                    

Several of the UV absorbers of the preceding examples were mixed into amethanol solution and the absorption maxima (λmax) and extinctioncoefficients (εmax) were calculated are listed in Table 2.

                  Table 2                                                         ______________________________________                                        Example    Max(nm)       εmax)                                        ______________________________________                                        A          377           6.60 × 10.sup.4                                B          377           6.50 × 10.sup.4                                C          373           6.30 × 10.sup.4                                D          377           6.65 × 10.sup.4                                E          377           5.90 × 10.sup.4                                F          376           6.54 × 10.sup.4                                H          376           6.10 × 10.sup.4                                I          362           5.75 × 10.sup.4                                M          362           6.35 × 10.sup.4                                N          372           6.20 × 10.sup.4                                O          372           6.53 × 10.sup.4                                P          371           6.94 × 10.sup.4                                ______________________________________                                    

EVALUATION OF PHOTOGRAPHIC COATINGS EXAMPLE 1

The UV compound of Example A above(3-dibutylaminoallylidenemalononitrile) was dispersed without auxiliarysolvent in a gelatin emulsion and coated to obtain coverage of 0.98 g/m²of dry gel and 0.27 g/m² of UV compound. This layer was coated onto acellulose acetate film support and the absorption (λmax) of the coatingwas found to be the same as in the methanol solution (377 nm).

EXAMPLE 2

The optical density of the U.V. compound of Example B(3-Dihexylaminoallylidenemalononitrile) was determined in a series ofcoatings. Example 2(b) was a no solvent/gelatin dispersion of the U.V.compound. Example 2(c) was a di-n-butyl phthalate/gelatin dispersion ofthe U.V. compound and Example 2(d) was a dispersion of the U.V. compoundin the form of a loaded latex, whereby the U.V. compound is contained inthe solid particles of a polymeric latex composition, prepared asdisclosed in the aforementioned Chen U.S. patent application Ser. No.506,919, filed Sept. 19, 1974. The dispersion of loaded latex particleswas prepared by dissolving 40.0 g of3-dihexylaminoallylidenemalononitrile in 700 cc. of acetone and thengradually stirring 1320 g. of the latex, poly(n-butylmethacrylate-co-2-acrylamido-2-methylpropane sulfonicacid-co-2-acetoacetoxy ethyl methacrylate (85:10:5), into the U.V.compound/solvent solution. The acetone was removed in 24 min. at 50° C.Example 2(a) was a coating of gelatin without the U.V. compound. Thefollowing optical densities were observed:

                  Table 3                                                         ______________________________________                                               Geletin Dye      Optical Densities                                     Example  g/m.sup.2 g/m.sup.2                                                                              370mm     415mm                                   ______________________________________                                        2(a)     0.54      --       0.08      0.05                                    2(b)     0.54      0.20     1.16      0.55                                    2(c)     0.54      0.20     1.60      0.42                                    2(d)     0.54      0.20     3.00      0.11                                    ______________________________________                                    

The above data demonstrates that a coating of gelatin and especially theloaded latex form of the U.V. compound-containing composition provideexcellent ultraviolet light absorbing properties with a very sharpcutoff at 415 nm at the same dye coverage.

EXAMPLE 3

A multilayer color negative coating was prepared as described in U.S.Pat. No. 3,046,129, column 25, line 67-column 26, line 20. Over theblue-sensitive layer of this coating was coated an ultraviolet absorbinglayer, comprising a loaded latex of the compound of Example B in thelatex of Example 2 (2.2 g in 40.0 g latex) prepared as described inExample 2. Sufficient gelatin was added to the dispersion so that thelayer contained 0.11 g/m² UV compound and 0.90 g/m² gelatin. Aprotective gelatin overcoat was coated over the ultraviolet absorbinglayer. A control coating, identical in all respects except that theultraviolet absorbing layer was omitted, was prepared. Samples of thecoatings were exposed in an Eastman 1B sensitometer to a simulateddaylight light source with no filter. Other samples were exposed to thesame light source through a Wratten 18A filter and still other sampleswere exposed through a Wratten 2A filter. The coatings were developed tocolor negatives in a process similar to that described in U.S. Pat. No.3,046,129, column 23, line 35-column 24, line 24.

The Wratten 18A filter transmits only ultraviolet radiation and infraredradiation. The Wratten 2A filter absorbs ultraviolet radiation to 405 nmbut transmits light at wavelengths beyond 405 nm. Table 4 shows thedifference in sensitivity (Δlog E) of the blue-sensitive layer betweenthe coating containing the ultraviolet absorbing compound and thecoating without the absorbing compound.

There was no difference in log E values of the coating exposed through aWratten 2A filter which shows that the ultraviolet compound is notabsorbing visible light. The difference in log E values of coatingsexposed through a Wratten 18A filter shows that the ultravioletabsorbing compound is absorbing ultraviolet light efficiently. The clearexposure shows that ultraviolet radiation contributes significantly tothe exposure of the control, which exposure is undesirable for goodcolor reproduction.

                  Table 4                                                         ______________________________________                                                Clear    Wratten 2A   Wratten 18A                                     ______________________________________                                        Δlog E*                                                                           -0.14      0.00         -1.85                                       ______________________________________                                         *log exposure of the bluesensitive layer of experimental coating  log         exposure of control                                                      

Similarly, a UV compound according to this invention can be incorporatedinto the support of a multilayer color negative material with excellentUV protection obtainable.

The invention has been described in detail with particular reference tocertain preferred embodiments thereof, but it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention.

We claim: .[.
 1. In a photographic element comprising a support, atleast one radiation sensitive silver halide emulsion layer and anultraviolet absorbing compound, the improvement comprising the use of a1-amino-4-cyano-1,3-butadiene ultraviolet absorbing compound..]. .[.2.The element according to claim 1 wherein said1-amino-4-cyano-1,3-butadiene compound is of the formula: ##STR26##wherein n is 1 or 2, when n is 1, R₁ and R₂ are independently chosen torepresent hydrogen, an alkyl group of 1 to 10 carbon atoms, an arylgroup of 6 to 20 carbon atoms, or a cyclic alkyl group of 5 or 6 carbonatoms provided that R₁ and R₂ cannot both be hydrogen, or R₁ and R₂taken together represent the atoms necessary to complete a cyclic aminogroup and when n is 2 at least one of R₁ and R₂ is alkylene or arylene,and G represents an electron withdrawing group..].
 3. A photographicelement comprising a support having thereon at least one radiationsensitive silver halide emulsion layer and an ultraviolet filter layercomprising a binder and at least one compound having the formula:##STR27## wherein n is 1 or 2, when n is 1, R₁ and R₂ are independentlychosen to represent hydrogen, an alkyl group of 1 to 10 carbon atoms, anaryl group of 6 to 10 carbon atoms, or a cyclic alkyl group of 5 to 6carbon atoms provided that R₁ and R₂ cannot both be hydrogen, or R₁ andR₂ taken together represent the atoms necessary to complete a cyclicamino group and when n is 2 at least one of R₁ and R₂ is alkylene orarylene, and G represents an electron withdrawing group.
 4. Aphotographic element according to claim 3 wherein the binder is ahydrophillic colloid.
 5. A photographic element according to claim 3wherein the electron withdrawing group is selected from the groupconsisting of ##STR28## where R represents an alkyl group of 1 to 10carbon atoms or aryl group of 6 to 10 carbon atoms.
 6. A photographicelement according to claim 3 wherein G is the group CN and R₁ and R₂ areboth alkyl groups of 1 to 10 carbon atoms.
 7. A photographic elementaccording to claim 3 wherein G is the group CN, R₁ is hydrogen and R₂ isan alkyl group of 1 to 10 carbon atoms.
 8. A photographic elementcomprising a support having thereon at least one silver halide emulsionlayer and at least one ultraviolet filter layer comprising a binder andat least one compound selected from the group consisting of3-dibutylaminoallylidenemalononitrile,3-dihexylaminoallylidenemalononitrile,3-tert-butylaminoallylidenemalononitrile,3-diisobutylaminoallylidenemalononitrile,3-di-sec-butylaminoallylidenemalononitrile,3-hexahydroazepinoallylidenemalononitrile, 3-N-(n-butyl)-N-cyanomethylaminoallylidenemalononitrile,3[N,N-bis-(2,2-diethoxyethyl)amino]allylidenemalononitrile,3(n-methyl-N-cyanomethyl)aminoallylidenemalononitrile, 1,4-piperazinobis(allylidenemalononitrile),N,N'-diethyl-N,N-di(4,4-dicyenobutadienyl)-1,6-diaminohexane and3[N,N-bis(2-cyanoethyl)amino]allylidenemalononitrile.
 9. A photographicelement comprising a support having thereon at least one silver halideemulsion layer and at least one ultraviolet filter layer comprising abinder and at least one compound selected from the group consisting of3-morpholinoallylidene methylsulfonylacetonitrile,3-morpholinoallylidene 4-tert-butylphenylsulfonylacetonitrile,3-piperazinoallylidene 4-tert-butylphenylsulfonylacetonitrile and3-N-methylpiperazinoallylidene 4-tert-butylphenylsulfonylacetonitrile.10. A photographic element comprising at least one silver halideemulsion layer coated on a film support, said film support beingselected from a solvent cast or melt-formed film support and havingincorporated therein at least one ultraviolet filter compound of theformula: ##STR29## wherein n is 1 or 2, when n is 1, R₁ and R₂ areindependently chosen to represent hydrogen, an alkyl group of 1 to 10carbon atoms, an aryl group of 6 to 10 carbon atoms, or a cyclic alkylgroup of 5 or 6 carbon atoms provided that R₁ and R₂ cannot both behydrogen, or R₁ and R₂ taken together represent the atoms necessary tocomplete a cyclic amino group and when n is 2 at least one of R₁ and R₂is alkylene or arylene, and G represents an electron withdrawing group.11. A photographic element according to claim 10 wherein the electronwithdrawing group is selected from the group consisting of ##STR30##where R represents an alkyl group of 1 to 10 carbon atoms or aryl groupof 6 to 10 carbon atoms.
 12. A photographic element according to claim10 wherein G is the group CN and R₁ and R₂ are alkyl groups of 1 to 10carbon atoms.
 13. A photographic element according to claim 10 wherein Gis the group CN, R₁ is hydrogen and R₂ is an alkyl group of 1 to 10carbon atoms.
 14. A photographic element comprising at least one silverhalide emulsion layer coated on a film support, said film support beingselected from a solvent-cast or melt-formed film support and saidsupport having therein at least one ultraviolet filter compound selectedfrom the group consisting of 3-dibutylaminoallylidenemalononitrile,3-dihexylaminoallylidenemalononitrile,3-tert-butylaminoallylidenemalononitrile,3-diisobutylaminoallylidenemalononitrile,3-di-sec-butylaminoallylidenemalononitrile,3-hexahydroazepinoallylidenemalononitrile,3-N(n-butyl)-N-cyanomethylaminoallylidenemalononitrile,3(N,N-bis-(2,2-diethoxyethyl)amino]allylidenemalononitrile,3(n-methyl-N-cyanomethyl)aminoallylidenemalononitrile, 1,4-piperazinobis(allylidenemalononitrile),N,N'-diethyl-N,N-di(4,4-dicyanobutadienyl)-1,6-diaminohexane and3-[N,N-bis(2-cyanoethyl)amino]allylidenemalononitrile.
 15. Aphotographic element comprising at least one silver halide emulsionlayer coated on a film support, said film support being selected from asolvent-cast or melt-formed film support and said support having thereinat least one ultraviolet filter compound selected from the groupconsisting of 3-morpholinoallylidenemethylsulfonylacetonitrile,3-morpholinoallylidene 4-tert-butylphenylsulfonylacetonitrile,3-piperazinoallylidene 4-tert-butylphenylsulfonylacetonitrile and3-N-methylpiperazinoallylidene 4-tert-butylphenylsulfonylacetonitrile.16. A photographic element comprising a support having thereon at leastone silver halide emulsion layer and at least one ultraviolet filterlayer comprising a binder and 3-dibutylaminoallylidenemalononitrile. 17.A photographic element comprising a support having thereon at least onesilver halide emulsion layer and at least one ultraviolet filter layercomprising a binder and 3-dihexylaminoallylidenemalononitrile.
 18. Aphotographic element comprising at least one silver halide emulsionlayer coated on a film support, said film support being selected from asolvent-cast or melt-formed film support and having therein theultraviolet filter compound 3-dibutylaminoallylidenemalononitrile.
 19. Aphotographic element comprising at least one silver halide emulsionlayer coated on a film support, said film support being selected from asolvent-cast or melt-formed film support and having therein theultraviolet filter compound 3-dihexylaminoallylidenemalononitrile..Iadd.20. A photographic element comprising a support having thereon atleast one radiation sensitive silver halide emulsion layer and anultraviolet filter layer comprising a binder and at least one compoundhaving the formula: ##STR31## wherein n is 1 or 2, when n is 1, R₁ andR₂ are independently chosen to represent hydrogen, an alkyl group of 1to 10 carbon atoms, or a cyclic alkyl group of 5 or 6 carbon atomsprovided that R₁ and R₂ cannot both be hydrogen, or R₁ and R₂ takentogether represent the atoms necessary to complete a cyclic amino groupand when n is 2 at least one of R₁ and R₂ is alkylene and G representsan electron withdrawing group. .Iaddend. .Iadd.21. A photographicelement comprising at least one silver halide emulsion layer coated on afilm support, said film support being selected from a solvent cast ormelt-formed film support and having incorporated therein at least oneultraviolet filter compound of the formula: ##STR32## wherein n is 1 or2, when n is 1, R₁ and R₂ are independently chosen to representhydrogen, an alkyl group of 1 to 10 carbon atoms, or a cyclic alkylgroup of 5 to 6 carbon atoms provided that R₁ and R₂ cannot both behydrogen, or R₁ and R₂ taken together represent the atoms necessary tocomplete a cyclic amino group and when n is 2 at least one of R₁ and R₂is alkylene and G represents an electron withdrawing group. .Iaddend.